Complex nitriles



Patented Aug. 23, 1949 UNITED. STATES PATENT OFFICE COMPLEX NITRILES Frank J. Gdavis, Elkins Park, Pa., assignor to Riihm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application April 28, 1948, Serial N0. 23,851

10 Claims. (01. 260-465) This invention deals with new condensates (a etoxymethy1)-6-c c1ohex 1 hen l a from oleonitrile and esters formed from methyl- 000C153 olphenols and lower carboxylic acids. It also concerns a method of preparing these conden- 061111 0320000118 sates. 5 i

In U. S. Patent No. 2,265,141, issued on December 9, 1941, it is shown that acyloxymethyl- CH2OCOCHa phenyl esters are prepared by heating aminomethylphenols with anhydrides of carboxylic zfi'bis(acemxymethyl)'4'benzylphenyl acetate acids. The amine group of aminomethylphenols 0900B is displaced and there result esters of the formula cmcoocm 011200 OCH:

( ACl)n (JJHzOAcz); 16 HzCsHs wherein Ar represents an aromatic hydrocarbon 4')acetxymgghgggphenylphenyl acetate nucleus, A01 and A02 are the acyl radicals of monocarboxylic acids, n is an integer from 1 to 2 in G H elusive, and :c is an integer from 1 to 4 inclusive. 20 5 01120 0 0 on, Ar may represent a single aromatic nucleus of the benzene series or several phenyl groups. The phenyl groups may contain hydrocarbon sub- C 00113 stituents such as alkyl, aralkyl, or cycloalkyl groups. Typical esters are 2-acetoxymethylphenyl acetate CH5C O O 0 o 0 CH3 H20 0 0 CH3 ornoo 00m and polynuclear structures such as omcoocm CHzOCOCH: 2,4-bis (acetoxymethyl) phenyl acetate CHiOCOCH: CH;--O-CH:

11100003 omoooon. cmocoon.

2,4,6-tris (acetoxymethyl) phenyl acetate and omcoo oaiocoom 000011 CHZOGOGH omocoom 2-acetoxymethyl--butylphenyl acetate 0 c 0 CH:

01110 c 0 OH:

.11, a c OCH;

In the above illustrations the groups represented generically by Am and A02 in the general formula are both shown as acetyl. The esters are not, however, to be limited to acetates; nor need the two sorts of acyl groups, Am and Acz, be identical. While it is best to have these groups acyl groups fr'cjrif Iogvenmonqcarboxync acids, particularly saturated aliphatic acids, of two to eight carbon atoms, the group An, which forms an ester with the phenolic hydroxyl group, may be different from A02 and be even larger than one of eight carbon atoms. As is known, sr'nall acyl groups may be replaced with larger a'cyl groups by transesterification, but this is not the Process or reaction here involved.

It has now been found that unsaturated ali-- phatic nitriles react with acyloxymethylpheny l esters to displace the acyloxy group. The reaction takes place at relatively high tempera tures, 270 C. to 360 C. being a suitable range of temperature; The unsaturated nitrile b'coines attached to the methylene radical from the acyloxymethyl group an d the acyloxy portion appears in a monocai'bbxylic' acid; which is distilled from the reaction mixture. For this reason the size of the acyl portion of the a'cyloxymethyl substituent is practically limited to eight carbon atoms. Since the acyl group A01 is not thus replaced; limitation of size or this" latter group is not essential.

An available unsaturated aliphatic nitrile which is particularly useful is oleonitrile, which is readily prepared from oleic acid by reaction with ammonia.

The products obtained by the reaction of oleonitrile and the aoyltixyme'thyl-substituted phenyl esters are exepiiefiaily li' bbil'ifig compounds which have thermal stabili y at elevated temperatures. The compounds in which the phenolic hydroxyl group is esterified with acetic or propionic acids remain liq'uidin the cold. They are thus useful as hydraulic fluids, lubricants, and solvents. The compounds of this invention are generally useful as softeners, plasticizers, and modifiers of resinous materials.

The following examples supply details of typical preparation of the bom'pounds of this invention.

sirdmize 1 To a reaction vessel, fitted with a thermometer and gas inlet tube in a long neck thereof and with a condenser from a) side ,arm, there was charged 70 parts by weight of 2,4,6-tris(acetoXymethyl) phenyl acetate and 158 parts of distilled oleonitrile. A slow stream of carbon dioxide was passed through the reaction mixture. This mixture was heated slowly to about 275 (3., when reaction began. The temperature of the vapor leaving the reaction vessel was 100 to 120 C. A distillate was collected which was found to be 95% acetic acid. This reaction mixture was heated up to 285 C. and heating was continued until no more vapors were taken off. At this point 0.59 mole of acetic ass had been collected, compared with 0.60 mole of acetic acid theoretically available from the three acetoxyn-iethyl groups. The reaction mixture was then stripped at 200 C. with the pressure b'eing reduced to one millimeter. About five parts :of distillate were obtained during this time with 178 parts of liquid remaining in the reaction vessel.

This liquid was examined for chemical and physica1 properties. It had a nitrogen content of 4.29% compared to the theoretical content for 4 the tricyano compound of 4.34%. Unsatura tion by bromine-absorption was 96.6% of theory for a tri-oleyl compound. The fluid had viscosities at 210 F., 100 F., and F. of 21.33 cs., 170.3 es, and 10,320 cs., respectively. This liquid has a viscosity index of 133. The viscosity at 0 F. is only 3% more than the value obtained by extrapolatiori of the viscositytemprature curve from 210 F. to 100 F. It may be noted that the starting materials have the following viscosities: oleonitrile, 2.23 cs. at 210 F. and 7.18 cs. at 100 F. with a viscosity index of 82; tris acetoxyirithyDphnyl acetate, 7.55 cs. at 210 F. and

123.1 cs. at 100 F. with a viscosity index of -64.

The compound prepared above was mixed with polyvinyl chloride and found to have a plasticizingaction. The 100% modulus of a mixture of 35% of the condensate and 65% of polyvinyl chloride was found to be 1440 p. s. i.; the Kemp bendbrittle point was --8 C.

teampie 2 The procedure of Example 1 was followed with amixture of one-half mole of 25acetoxymethylphenyl acetate and one-half mole of oleonitrile. The reaction temperature was carried to 360 C. The liquid obtained was non-volatile at 200 6. under one millimeter pressure; It hadaviscosity 016,89 cs. at 210 F; and; 56 cs: at 1 00 F.-

In place of the acetate grpups in the above acyloxymethylphenyl esters, there maybe used propionates, butyrates, or octoates. The acyl group of the acyloxymethylsubstituent need not be the same as that which fdrms an ester grouping with the phenolic hydro'xyl group, as shown in U. S. Patent No. 2,306,932, issued December 29, 1942. Thus, the phenolic hydroxyl group of anaminomethylphenol may be esterified with anacyl halide, the acyl group of which differs from that of an acid anhydride used to displace amine groupsin the aminometh ylphenol or its ester. In this way there are formed such compounds as I oHlooooHQ Qomoooorn Estate 3' A mixture of 67.5 grams of 2,4,6-tris(dimethylaminomethyl) phenol and 247 grams of Z-ethylhexoic anhydride was heated 'for ten hours at C. The 2,-ethylhexoic anhydride was prepared from Z-ethylhexoiotgid and acetic anhydride and was distilled at -160 C./30 mm. After the above reaction mixture had been heated for the ten-hour period, a forerun was removed up to 200 C./1 mm-.-, leaving a dark, gel-like residue. To this residue was added 40 grams (0.15 mole) of oleonitrile. Themixture was then placed in a Claisen flask fitted with a gas-inlet tube and a thermometer in the long neck, a thermometer in the short neck, and at the side-arm a condenser set for downward distillation. Nitrogen was then passed through the reaction mixture and the batch heated to 270280 C., at

which point it was held for three hours while four grams of distillate were collected upto a distillation temperature of about 120 C./atm. The nitrogen was then shut ofi and the system placed under reduced pressure while 35 grams of distillate were collected at 140-145 C./30 mm. This distillate contained 23.2 grams (theoretical value is 22 grams) of 2-ethylhexoic acid by titration. Redistillation of this acid showed the boiling point to be 225230 C./atm.', with the boiling point of Z-ethylhexoic acid reported as 226.9 C. The oleonitrile reaction product was a black solid residue. It corresponded in composition to the compound -OOO (NC 0111132) CH2 CH2(Ci1Ha2C CHawnHnCN) Example 4 2,4,6-tris- (dimethylaminomethyl) phenol 66 2-ethylhexoyl chloride 41 As the chloride was .added to the phenol, a solid formed (probably the amine hydrochloride).

Nevertheless, the batch was held at 8090 C. for

one-half hour. No hydrogen chloride was evolved. After the heating period 120 grams of acetic anhydride was added and the batch was refluxed for three hours. The solution became homogeneous and clear during this reflux period. At the end of the reflux period, the low-boiling materials were stripped oil on a water pump, after which the system was evacuated by an oil pump and the distillation carried out. A main fraction of 69 grams (64% of the theoretical) was 'collected at 230-240 C./1 mm. This material has poor viscosity-temperature properties, having a 210 F. viscosity of 6.761 05., a 100 F. viscosity of 104.9 cs., and a viscosity index of -92. This product was identified as 2,4,6-tris(acety1oxymethyl) phenyl Z-ethylhexoate. Sixty-one grams of this triacetate was mixed with 31 grams (0.12 mole) of oleonitrile in the same apparatus described in the first example. Nitrogen gas was passed through the system. With the reaction mixture heated at 300-315 C., 14.4 grams of distillate was collected at a distillation temperature of 108130 C. This distillate contained 0.11 mole of acetic acid. The residue set to a solid on cooling. It corresponded in composition to 2,4,6-tris (cyanooctadecenyl) phenyl Z-ethylhexoate.

The reaction which takes place corresponds to the following:

wherein Aci represents an acyl group, preferably of not over eight carbon atoms, and Acz represents an aliphatic acyl group of two to eight carbon atoms. The --CH2C1'IH32CN group has a cyano group in a terminal position.

When a derivative of phenol is at hand, the starting material has the formula (OHzOAcr) v where y is an integer from one to three inclusive. The derivatives of phenol are of particular interest.

I claim:

1. A process for preparing cyanooctadecenylphenyl esters of monocarboxylic acids of two to eight carbon atoms, which comprises heating together at 270 to 360 C. oleonitrile and a compound of the formula wherein Ar is an aromatic hydrocarbon nucleus, A01 and Acz are acyl radicals of monocarboxylic acids of two to eight carbon atoms, n is an integer from one to two inclusive, and m is an integer from one to four inclusive, the CHaOACa group occurring only in positions which are ortho and para to theOAc1 group.

2. A process for preparing cyanooctadecenylphenyl esters of saturated aliphatic monocarboxylic acids of two to eight carbon atoms, which comprises heating together at 270 to 360 C. oleonitrile and a compound of the formula (GHQOO 0011;),

wherein A01 represents the acyl radical of a saturated aliphatic monocarboxylic acid of two to eight carbon atoms and 1/ represents an integer from one to three inclusive, and oleonitrile in an amount substantially equivalent to the --CH2OCOCH3 portion of said compound, the CH2OCOCH3 group occurring only in positions which are ortho and para to the OACJ. group.

4. A process for pre ringtriseyanooeta decenynphenyr acetate, which com rises Heating together at 270" tQ-SGWQ; onemoieeuiar-pro portion of a compound of the formula 00 OGHr CHaCOOCH-r CHaOCOCHa and three molecular proportions of oleonitrile.

5.- A process for preparing 2-eyanooctadece-nyl-- phenylacetate, which comprisesheatingto'gether at 270 to 360 C. equimolecular proportions: of 2-acetoxymethylphenyl acetate and oleonitrileq 6. As a new chemical compound, Z-(cyanooctadecenyI) phenyl acetate, having. the formula.

(ROGUE:

(CHa-CuHazCN) wherein y is an integer from; one to three inclusive, the CHz-CrzHazCN group occurring only in positions which are ortho and para to the OCOCH: group; said compounds being those obtained by reacting together by heating at 270' to 360 C. an acyloxymethylphenyl ester of. amonocarboxylic acid of two to eight carbon atoms and. oleonitrile.

9. As new chemical compounds, cyanoocta= decenylphenyl esters of the formula wherein y' is an integer. from one to three inelusive and Acr is an acyl group of a saturated aliphatic monocarboxylic acid of two to eight carbon atoms, the CHz-C'wmzCN group occurring only in positions which are ortho and. para to the OAc1 group, said compounds being those obtained by reacting together by heating at 270 to 360 C. an acyloxymethylphenyl ester of a monocarboxylic acid of two to eight carbon atoms and oleonitrile.

10. As new chemical compounds, cyanooctadecenylphenyl esters of the formula (OAcO' (HZCflHtQCN); wherein A01 is an acyl group of a saturated aliphatic monocarboxylic acid of two to eight carbon atoms, 12 is an integer from one to two inclusive, a: is an integer from one to four inclusive, and Ar is an aromatic hydrocarbon nucleus, the CH2'C1'IH32CN group occurring only in positions which are orthoand para to the OAcz group, said compounds being those obtained by reacting together by heating at 270 to 360 C. an acyloxymethylphenyl ester of a monocarboxylic acid of two to eight carbon atoms and oleonitrilel FRANK J. GLAVISM REFERENCES CITED UNITED STATES PATENTS Name Date Bruson Dec. 9, 1941 OTHER REFERENCES Vorlander, Beilstein (Handbuch, 4th ed.) vol. 10, page 298 (1927).

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